Copper azides

Copper forms two azides cuprous azide or copper (I) azide, and cupric azide or copper (II) azide. Cuprous azide, Cu2(Nb)2, MW 211.14, CAS [14336-80-2] is a colorless crystalline solid. It is highly sensitive to impact. It explodes on heating. It decomposes at 205°C (401°F). The heat of formation [AH (i)] is reported as 253.1 kJ/mol (60 kcal/mol) (Bretherick 1995). 

Violent explosion can occur when this substance is subjected to shock or friction. Scratching the crystals out from the containers may result in explosion. It can detonate when dry. It may even explode when moist. 

Both azides can readily form explosive products when combined with acids, halogens, halogen oxides, ammonia, or heavy metal salt solutions. Cupric azide has limited use as a powerful initiator. It is a DOT-classified forbidden substance Hazard Label Forbidden. 

Documentation of the Threshold Limit Values and Biological Exposure Indices, 5th ed. Cincinnati, OH American Conference of Governmental Industrial Hygienists. 

Infrared studies of azide bound to myoglobin and hemoglobin temperature dependence of ionic-ity. Biochemistry 11 842. 

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I. Kabek and S. Urman, "Hazards of Copper Azide ia Fuzes," ia Minutes of the 14th Annual Explosives Safety Seminar, NTIS, 1972, p. 533. 

Reaction of acyl peroxides with copper azide... 

Lead azide (PbN6) is a colorless to white crystalline explosive. It is widely used in detonators because of its high capacity for initiating secondary explosives to detonation. However, since lead azide is not particularly susceptible to initiation by impact, it is not used alone in initiator components. It is used in combination with lead styphnate and aluminum for military detonators, and is used often in a mixture with tetrazene. It is compatible with most explosives and priming mixture ingredients. Contact with copper must be avoided because it leads to formation of extremely sensitive copper azide. 

Sh. Okubo, K. Shindo S. Oinuma, Copper Azide Detonators. I. Preparation of Copper Azide and Its Impact Sensitivity Test , TKShH 52,311-14 (1957) CA 52, 8559... 

Comp C-1 Copper Copper acetanarsenate Copper azide Copper carbonate Copper chloride Copper fulminate Copper oxide Cryolite ... 

CNTA Comp C-1 Copper azide Copper fulminate 5-Nitroterazole copper salt... 

Different types of initiatory explosives essentially developed for military applications have also been used for commercial detonators and cap compositions. Service lead azide (SLA) has been extensively used as an initiatory explosive for detonators. However, it has the limitation that hydrazoic acid forms on ageing and ultimately forms sensitive copper azide with copper tube-based detonators (responsible for many unfortunate accidents all over the globe) therefore SLA has been replaced by a new and safe initiatory explosive known as basic lead azide (BLA). 

Cirulis (Ref 13) found that LA loaded into copper caps can form copper azide if moisture is present. Hydrazine and hydroxylamine reduce Cu(N3), to white, cuprous azide, CuN,... 

Cupric Amminoazide (Ammoniate of Copper Azide), Diammine copper azide, [Cu(NHj)a] (Nj)a, mw 181.65, N 61.69% green crysrs, expl when heated or struck. Obtained by Dennis Isham (Ref 2) by shaking freshly pptd black cupric hydroxide, while still moist, with ao excess of hydrazoic acid, and washing and dissolving the ppt in aq ammonia. This compd was also prepd by Browne et al (Ref 6) and studied by Strecker Schwinn (Ref 8) and by Straumanis Cirulis (Ref 11) (See also Ref 21, p 149 and Table D under Ammines in this dictionary). Tetrammine copper azide, [Cu(NHs),](N3)a, mw 215.72, N 64.90%, blue crysts, expl at 202° and on impact. Prepd by Strecker Schwinn (Ref 8) and by Straumanis Cirulis (Ref 11) from cupric azide and NHS, (either liq or the dry gas). Only the di- and tetrammino- compds were prepd, (See also Ref 21, p 149 and Table D under Ammines)... 

The copper azide chloride, Cu(N3)a-3CuCla 6H,0 or Cu(Nj)a 3CuCla prepd by Straumanis Cirulis (Ref 16) expl at 207-8°. The hydrate cannot be dehydrated. Therefor the anhyd compd should be prepd from abs ale The general types of copper azide addn compds a)[Cu(N,) ] b)[Cu(N3)J c)... 

Kwart and Kahn have found that benzenesulfonyl azide forms a complex with freshly reduced copper powder.189 190 This copper azide complex decomposes at a lower temperature than the pure sulfonyl azide. In refluxing methanol, benzene-sulfonamide (27) is isolated as the major product. In the presence of dimethyl sulfoxide, N-benzenesulfonyldimethyl-sulfoximine (28) is obtained in almost quantitative yield. In cyclohexene solution benzenesulfonamide (29), N-benzenesul-fonyl-7-azabicyclo[4.1.0]heptane (30), and 1-cyclohexenylben-zenesulfonamide (31) are isolated as the main reaction products. According to the authors, Schemes VII and VIII represent an acceptable interpretation of the experimental data.189 190 In pure alcohol, the decomposition should occur by two competitive reactions (Scheme VII) producing benzenesulfonamide together with a ketone and oxidized copper. These last two products have indeed been observed in the reaction mixture. In the presence of DMSO, it seems that a copper-nitrene intermediate is formed which is trapped by DMSO. In cyclohexene solution, the authors have observed that the aziridine (30) disappears from the product composition when DMSO is added. The yield of enamine 31, however, is... 

Copper Azide Explosive Complexes of Cirulis Straumanis. The following complexes are listed Gmelin (Ref 4). Their prepns are described in Refs 1, 2, or 3... 

See also Cupric Azide Complexes, Vol 1, p A533-L and the Copper Azide Explosive Complexes of Cirulis Straumanis in this Vol, p C 5 17-R... 

CuN3 (c). Wohler and Martin1 measured the heat of decomposition of copper azide to be 56.8. 

Chromyl azide, 4233 Cobalt(II) azide, 4210 Copper azide, 4281 Copper(II) azide, 4274... 

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